Star block copolymer

ABSTRACT

A novel star block copolymer which can be made to have a high molecular weight and gives a solution having a lower viscosity than solutions of linear polymers having the same molecular weight as the copolymer and which is expected to be used as a resist material; and a process for producing the copolymer. The star block copolymer having alkenylphenol skeletons is obtained by homopolymerizing by living anion polymerization an alkenylphenol compound in which the hydroxyl group of the phenol moiety has been protected by a saturated aliphatic protective group or copolymerizing the alkenylphenol compound with a vinylaromatic compound by living anion polymerization, subsequently copolymerizing the resultant polymer using a polyfunctional coupling agent such as divinylbenzene to obtain a star block copolymer, and eliminating the saturated aliphatic protective groups with an acid reagent.

RELATED APPLICATION

This application claims the benefit of International ApplicationPCT/JP00/05919 filed Aug. 31, 2000 and which published in the Japaneselanguage with an English abstract only as WO 01/16198 on Aug. 3, 2001.

TECHNICAL FIELD

The present invention relates to a star block copolymer with an armmoiety having an alkenylphenol homopolymer or copolymer as polymerchains and a process for producing the same. The star block copolymer ofthe present invention is a compound anticipated to be utilized as aresist material for excimer lasers and electron beams.

BACKGROUND ART

Alkenylphenol homopolymers and copolymers of which poly-p-hydroxystyreneis a representative are useful as resist materials for excimer lasers ofchemical amplification. Among them, resists using apoly-(p-hydroxystyrene) or (p-hydroxystyrene/styrene) copolymer areknown as resists capable of imaging with high resolution.

In regards to star block copolymers, for example, in Japanese UnexaminedPatent Publication No. 222114 of 1993, a star polymer has been describedin which a block copolymer molecule is produced by anionicpolymerization of isoprene and styrene, coupled with a polyalkenylcoupling agent at 2.5 moles or more per 1 mole of the block copolymermolecule, and further 95% or more of isoprene units (olefin unsaturated)and less than 15% of styrene units (aromatic unsaturated) areselectively hydrogenated.

Japanese Unexamined Patent Publication No. 220203 of 1994 has describeda modified block copolymer comprising a core crosslinking with apolyfunctional coupling agent, and comprising at least one type ofpolymer block induced from unsaturated carboxylate ester of alkyl, andat least one type of polymer block induced from conjugated diene and/orat least one type of a polymer block induced from monovinyl aromaticcompound.

Japanese Unexamined Patent Publication No. 256436 of 1994 has describeda polymer comprising at least three first arms with peak molecularweight of from 10,000 to 200,000 comprising hydrogenated polymerizationconjugated diene; at least three second arms with peak molecular weightof from 500 to 10,000 comprising polymerized methacrylate and/or anamido or imide derivative thereof; and a central core connecting thefirst arms and second arms in a star configuration and comprisingpolymerized bis unsaturated monomer.

Japanese Unexamined Patent Publication No. 97413 of 1995 has described astar block polymer having the general formula:

wherein C is a block of crosslinked bis unsaturated monomer; each A isindependently a block of anionic polymerization monomer; M is a block ofpolymerization methacrylic acid alkyl polymerized through ethyleneunsaturation of methacrylic acid moiety; r is 0 or 1; and s and t are anaverage of 2 or more but s≦t wherein the molecular weight of from 20,000to 2,000,000 and A is styrene or isoprene.

Japanese Unexamined Patent Publication No. 48987 of 1996 has described astar polymer having the structure represented by (EP′-S-EP″) n-X whereinEP′ is a first hydrogenated block of polyisoprene (I′) with the numberaverage molecular weight (Mn) before hydrogenation of from 10,000 to100,000, S is polystyrene block with the average molecular weight (Mn)of from 6,000 to 50,000, EP″ is a second hydrogenated block ofpolyisoprene (I″) with the number average molecular weight (Mn) beforehydrogenation of from 2,500 to 50,000, a molecular ratio of I′/I″ is atleast 1.4, X is a core consisting of a polyalkenyl coupling agent, and nis an average arm number per star molecule formed by reacting thepolyalkenyl coupling agent at 2 moles or more for one mole of(EP′-S-EP″), wherein the star polymer consists of an intramolecularbound polystyrene block and hydrogenated polyisoprene block and isuseful as an improver of the viscosity index (VI).

Japanese Unexamined Patent Publication No. 81514 of 1996 has described apolyfunctional initiator of anionic polymerization, which is soluble innon-polar solvents, not containing (or substantially not containing) anyresidual double bond and represented by the general formula,(PA)_(a)N^(r.−)nLi⁺ wherein PA represents a polymer block generated fromat least one type of monomer A selected from vinyl aromatic monomers anddiene monomers; a represents a number of arms of PA block, from 3 to 30,especially from 3 to 15; N represents a crosslinked core not containingor substantially not containing any residual double bond and has theformula, (PMc) (RLi) p wherein Mc is a monomer containing at least twopolymerized double bonds per molecule; PMc is a crosslinked core of atleast one type of polymerization monomer Mc containing from 3 to 30%residual double bonds for initial double bonds derived from monomer Mc;R is an alkyl group and the like having straight or branched chains; andp is a number of residual double bonds in PMc neutralized with RLi; n isa number of anion sites present in the crosslinked PMc core and equal toa+p (or p) (p has the above meanings, and a is a number of anion sitespresent in the crosslinked core before addition of RLi.)

Japanese Patent Publication No. 504865 of 1996 has described a starblock copolymer comprising (a) at least three arms from at least oneanion polymerized monomer selected from the group consisting ofmonovinyl aromatic hydrocarbon, conjugated diene and the mixturesthereof, (b) at least three arms comprising polydimethyl siloxane and(c) a core comprising a polyalkenyl aromatic coupling agent (the above(a) and (b) radiate out from this core).

Published Japanese Translation of PCT International Publication forPatent Applications No. 505179 of 1996 has described a block copolymerof the general formula (A-B)n(B) mX wherein A is a block of polystyrenehaving peak molecular weight of less than 15,000, B is a polymer blockof hydrogenated conjugated diene having peak molecular weight rangingfrom 15,000 to 50,000, X is a block of divinylbenzene, and n and m areintegers of 0 or more wherein a sum of n and m is at least 10.

Published Japanese Translation of PCT International Publication forPatent Applications No. 510236 of 1997 has described a star copolymercontaining (a) four molecules or more of polyfunctional binders forminga core selected from the group consisting of divinyl aromatic compound,trivinyl aromatic compound, diepoxide, diketone, and aldehyde; and (b)three or more of cation polymer branches bound to said core wherein saidpolymer branch is selected from the group consisting of a homopolymer,copolymer and block copolymer having at least one polyolefin segment andat least one polyaryl segment, and a graft copolymer.

DISCLOSURE OF THE INVENTION

Polymers with higher molecular weights have been conventionally known tobe more preferable as base polymers for positive resist materials interms of resolution, heat resistance and the like. However, when amolecular structure of a base polymer is accompanied with high molecularweight as a conventional linear structure, it has been problematic inthat resist viscosity is increased resulting in difficulty of spincoating though resist application on substrates is usually performed byspin coating.

Among the star block copolymers described above, those having ahydroxystyrene skeleton at an arm moiety have not been known.

The subject of the present invention is to provide a novel star blockcopolymer which can be made to have a high molecular weight as asolution and has a lower viscosity than solutions of linear polymershaving the same molecular weight as the copolymer and which is expectedto be used as a resist material; and a process for producing thecopolymer.

As results of an intensive study to achieve said subject, the presentinventors have found that the star block copolymer with a narrowmolecular weight range having alkenylphenol skeletons of which structureis controlled is obtained by homopolymerizing by living anionicpolymerization an alkenylphenol compound in which the hydroxyl group ofthe phenol moiety has been protected by protective groups orcopolymerizing the alkenylphenol compound with a vinylaromatic compound,subsequently copolymerizing the resultant polymer using a polyvinylcompound to obtain a star block copolymer, and eliminating phenolhydroxyl protective groups with an acid reagent, and then completing thepresent invention based on these findings.

That is, the present invention relates to the star block copolymerdescribed in any of the following (1) through (19):

(1) the star block copolymer characterized by having an arm moietycomprising a central core and a polymer chain radiated out from thecentral core, wherein the arm moiety (A) comprises the polymer chain(A1) having a repeated unit represented by the general formula (I):

wherein R₁ represents a hydrogen atom or a methyl group; R₂ represents ahydrogen atom or a C1-C6 alkyl group; and p represents 1 or 2 wherein R₂may be identical or different when p is 2;

(2) the star block copolymer according to (1) characterized in that thepolymer chain (A1) is a copolymer having repeated units represented bythe general formula (I) and (II):

wherein R₃ represents a hydrogen atom or a methyl group; R₄ represents ahydrogen atom or a C1-C6 alkyl group; R₅ represents anacidolytic/leaving group; q represents 1 or 2 wherein R₄ may beidentical or different when q is 2;

(3) the star block copolymer according to (1) characterized in that thepolymer chain (A1) is a copolymer having repeated units represented bythe general formula (I) and (III):

wherein R₆ represents a hydrogen atom, a methyl group, or an aryl groupwhich may have substituents; R₇ represents a hydrogen atom or a C1-C6alkyl group; r represents 1 or 2 wherein R₇ may be identical ordifferent when r is 2;

(4) the star block copolymer according to (1) through (3) characterizedin that the polymer chain (A1) have repeated units represented in thegeneral formula (I), (II) and (III) wherein R₃, R₄, R₅, and q are thesame as mentioned above;

(5) the star block copolymer according to any of (1) through (4)characterized in that the arm moiety (A) has the polymer chain (A1) anda polymer chain (A2) having a repeated unit (A21) represented by thegeneral formula (IV):

wherein R₈ represents a hydrogen atom or a methyl group; R₉ represents ahydrogen atom, a C1-C12 alkyl group, a hydrocarbon group having C3 ormore alicyclic skeletons which may have substituents, an alkyl grouphaving hydrocarbon groups having the alicyclic skeletons, or aheterocyclic group;

(6) the star block copolymer according to (5) characterized in that thepolymer chain (A2) has the repeated unit (A21) represented by thegeneral formula (IV) and a repeated unit (A22) represented by thegeneral formula (V):

wherein R₁₀ represents a hydrogen atom, a methyl group, or an aryl groupwhich may have substituents; R₁₁ represents a hydrogen atom, a C1-C6alkyl group, OR₁₂ group wherein R₁₂ represents a hydrogen atom, a C1-C6alkyl group, or acidolytic/leaving group; t represents an integer of 0or any of 1 through 3 wherein R₁₁ may be identical or different when tis 2 or more.

(7) the star block copolymer according to (6) characterized in that thepolymer chain (A2) is a block copolymerized by (A22) through (A21)sequentially from the central core;

(8) the star block copolymer according to any of (1) through (7)characterized in that the number average molecular weight of the polymerchains composing the arm moiety is in the range of from 1,000 to 100,000and a ratio (Mw/Mn) of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) is in the range of from 1.00 to1.50;

(9) the star block copolymer according to any of (1) through (8)characterized in that the central core is the core crosslinked with apolyfunctional coupling agent;

(10) the star block copolymer according to (9) characterized in that thepolyfunctional coupling agent is the compound having at least twopolymerization double bonds per molecule;

(11) the star block copolymer according to (9) or (10) characterized inthat the polyfunctional coupling agent is the compound represented bythe general formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆R₁₇N wherein R₁₆ and R₁₇ eachindependently represent hydrogen atoms, C1-C6 alkyl groups oralkoxycarbonyl groups, a methylene group which may have substituents, aphenylene group which may have substituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S,C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉), SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) (wherein R₁₈,R₁₉ and R₂0 represent C1-C6 alkyl groups, or phenyl groups which mayhave substituents), OCO, or CO₂CH₂; w represents an integer of 0 or 1 to2 wherein Y may be identical or different when w is 2; and u represents2 or 3 wherein Y, R₁₃ and w may be identical or different;

(12) the star block copolymer according to any of (1) through (11)characterized in that the number average molecular weight is from 3,000to 300,000;

(13) the star block copolymer according to any of (1) through (12)characterized in that the ratio (Mw/Mn) of the weight average molecularweight (Mw) to the number average molecular weight (Mn) is in the rangeof from 1.00 to 1.50; and

(14) the process for producing the star block copolymer according to anyof (1) through (13) characterized in that by an anionic polymerizationmethod using an anionic polymerization initiator as a polymerizationinitiator, the compound represented by the general formula (VII):

wherein R₃, R₄, R₅ and q are the same as mentioned above, ishomopolymerized or copolymerized with the compound capable ofcopolymerizing the compound represented by the general formula (VII),subsequently the polyfunctional coupling agent (C) is copolymerized andthe protective groups of phenol hydroxyl groups are eliminated;

(15) the process for producing the star block copolymer according to anyof (1) through (13) characterized in that by an anionic polymerizationmethod using an anionic polymerization initiator as a polymerizationinitiator, the compound represented by the general formula (VII) whereinR₃, R₄, R₅ and q are the same as mentioned above, is homopolymerized orcopolymerized with the compound capable of copolymerizing the compoundrepresented by the general formula (VII), subsequently copolymerizedwith the polyfunctional coupling agent (C), further copolymerized withthe compound capable of anion polymerizing, and then the protectivegroups of phenol hydroxyl groups are eliminated;

(16) the process producing the star block copolymer according to (14) or(15) characterized in that a molar ratio [(C)/(D)] of the polyfunctionalcoupling agent (C) to an active end of the polymer chainhomopolymerizing the compound represented by the general formula (VII)or an active end (D) of the polymer chain copolymerizing the compoundcapable of copolymerizing with the compound represented by the generalformula (VII) by the anionic polymerization method using the anionicpolymerization initiator as the polymerization initiator, is from 1.0 to10;

(17) the process for producing the star block copolymer according to anyof (14) through (16) characterized in that the polyfunctional couplingagent is a compound represented by the general formula (VI):

wherein Y, R₁₂, R₁₃, w and u are the same as mentioned above;

(18) the process for producing the star block copolymer according to anyof (14) through (17) characterized in that the compound capable ofcopolymerizing with the compound represented by the general formula(VII) is a compound represented by the general formula (IX):

wherein R₆, R₇, and r are the same as mentioned above; and

(19) the process for producing the star block copolymer according to anyof (15) through (17) characterized in that the compound capable of anionpolymerizing is a compound represented by the general formula (IX):

wherein R₈ and R₉ are the same as mentioned above.

The star block copolymer of the present invention is not limited so longas the polymer chain comprises the polymer chain (A1) having therepeated unit represented by the general formula (I) in the arm moiety(A) in the star block copolymer having an arm moiety comprising acentral core and a polymer chain radiated out from the central core,wherein in the repeated unit represented by the general formula (I), R₁represents a hydrogen atom or a methyl group; R₂ represents a hydrogenatom or C1 through C6 alkyl group wherein, specifically, methyl group,ethyl, isopropyl and t-butyl groups can be exemplified; p represents 1or 2 wherein R₂ may be identical or different when p is 2 whereinsubstituted sites of R₂ and the hydroxyl group (OH-group) are notespecially limited but the hydroxyl group is preferably substituted atthe para- or meta- position of an alkenyl group.

The above polymer (A1) chain is preferably copolymer having the repeatedunit represented by the general formula (I) and the repeated unitrepresented by the general formula (II). The molar ratio of the repeatedunit represented by the general formula (I) to the repeated unitrepresented by the general formula (II) in this polymer chain (A1) isnot specifically limited but the ratio [general formula (I)/generalformula (II)] is in the range of from 99/1 to 50/50, and preferably from95/5 to 60/40. In the repeated unit represented by the above generalformula (II), R₃ represents a hydrogen atom, a methyl group or an arylgroup which may have substituents. Specifically, phenyl, p-tolyl,4-methoxyphenyl groups and the like can be exemplified. Also, R₄represents a hydrogen atom or a C1 through C6 alkyl group. Specifically,methyl, ethyl, isopropyl, t-butyl groups and the like can beexemplified. The letter, q represents 1 or 2 wherein R₄ may be identicalor different when q is 2. The substituted sites of R₄ and the alkoxygroup (OR₅-group) are not specifically limited but the alkoxy group ispreferably substituted at the para- or meta- position of alkenyl group.

R₅ represents an acidolytic/leaving group. Acidolytic/leaving groupsherein mean the groups which leave or decompose by acids. Specifically,methoxymethyl, 2-methoxyethoxymethyl, bis(2-chloroethoxy)methyl,tetrahydropyranyl, 4-methoxy tetrahydropyranyl, tetrahydrofuranyl,triphenylmethyl, trimethylsilyl, 2-(trimethylsilyl) ethoxymethyl,t-butylmethylsilyl, trimethylsilylmethyl, t-butyl, t-butoxycarbonyl,t-butoxycarbonylmethyl, 2-methyl-2-t-butoxycarbonylmethyl groups and thelike can be exemplified. Furthermore, as R₅, the groups represented bythe following formula:

wherein R₁₄ represents the C1 through C20 alkyl group unsubstituted orsubstituted with alkoxy, C5 through C10 cycloalkyl group, or C6 throughC20 aryl group unsubstituted or substituted with alkoxy; R₁₅ representsa hydrogen atom or C1 through C3 alkyl group; and R₁₆ represents C1through C6 alkyl group or C1 through C6 alkoxy group. As suchsubstituents, specifically, 1-methoxyethyl, 1-ethoxyethyl,1-methoxypropyl, 1-methyl-1-methoxyethyl, 1-(isopropoxy)ethyl groups andthe like can be exemplified.

Also, the above polymer chain (A1) is preferably a copolymer having therepeated unit represented by the general formula (I) and the repeatedunit represented by the general formula (III). In the repeated unitrepresented by the formula (III), R₆ represents a hydrogen atom or amethyl group; R₇ represents a hydrogen atom or C1 through C6 alkylgroup, specifically methyl, ethyl, isopropyl, t-butyl groups and thelike can be exemplified; and r represents 1 or 2 wherein R₇ may beidentical or different when r is 2 wherein the substituted site is notespecially limited. The molar ratio of the repeated unit represented bythe general formula (I) to the repeated unit represented by the generalformula (III) in this polymer chain (A1) is not especially limited butthe ratio [general formula (I)/general formula (III)] is preferably inthe range of from 99/1 to 50/50.

Additionally, the above polymer chain (A1) is preferably a copolymerhaving the repeated units represented by the general formulae (I), (II)and (III). The molar ratio of the repeated units in this polymer chain(A1) is not especially limited but the molar ratio [general formula(I)/general formula (II)+general formula (III)] is preferably in therange of from 99/1 to 50/50.

The above arm moiety (A) preferably has the polymer chain (A2) havingthe polymer chain (A1) and the repeated unit (A21) represented by thegeneral formula (IV). In the repeated unit represented by the generalformula (IV), R₈ represents a hydrogen atom or a methyl group. R₉represents a hydrogen atom, C1 through C12 alkyl group, a hydrocarbongroup having alicyclic skeletons of C3 or more which may havesubstituents (but, do not include a carbon of substituents in carbonnumber), an alkyl group having hydrocarbon groups having the alicyclicskeletons, or heterocyclic group wherein acidolytic/leaving group ispreferable, and the group having t-butyl groups which can beleft/decomposed by acids is more preferable. Acidolytic/leaving groupsherein mean the groups which decompose and/or leave by acids.

As the above R₉, specifically, methyl, ethyl, n-propyl, isopropyl,n-butyl, t-butyl, methoxymethyl, 2-methoxyethoxymethyl,bis(2-chloroethoxy)methyl, tetrahydropyranyl,4-methoxytetrahydropyranyl, tetrahydrofuranyl, triphenylmethyl,trimethylsilyl, 2-(trimethylsilyl)ethoxymethyl, t-butyldimethylsilyl,trimethylsilylmethyl and the functional groups represented by thefollowing formulae wherein u represents 0 or 1 can be exemplified.

Further, as R₉, the groups represented by the following formula whereinR₁₇ represents C1 through C20 alkyl unsubstituted or substituted withalkoxy, C5 through C10 cycloalkyl, or C6 through C20 aryl unsubstitutedor substituted with alkoxy; R₁₈ represents a hydrogen atom or C1 throughC3 alkyl; and R₁₉ represents a hydrogen atom, C1 through C6 alkyl, or C1through C6 alkoxy groups, can be specifically exemplified. As suchsubstituents, specifically 1-methoxyethyl, 1-ethoxyethyl,1-methoxypropyl, 1-methyl-1-methoxyethyl, 1-(isopropoxy) ethyl can beexemplified.

The repeated unit in the polymer chain (A) having the repeated unit(A21) represented by the general formula (IV) may be alone or a mixtureof two or more, and in the case of a mixture of two or more, it is notespecially limited and may be bound by random or by a block. Further, insuch a case, the molar ratio is not especially limited, but in the caseof a mixture of two, any of the ratios ranging from 1/9 to 9/1 can beemployed.

The above polymer chain (A2) is preferably one having the repeated unit(A21) represented by the general formula (IV) and the repeated unit(A22) represented by the general formula (V). The molar ratio of (A21)through (A22) in this polymer chain (A2) is not especially limited butthe ratio [(A21)/(A22)] is of from 5/95 to 100/0, preferably in therange of from 50/50 to 99/1. In the repeated unit represented by theabove general formula (V), R₁₀ represents a hydrogen atom, a methylgroup or an aryl group which may have substituents and specifically,phenyl, p-tolyl, 4-methoxyphenyl groups and the like can be exemplified.R₁₁ represents a hydrogen atom, C1 through C6 alkyl or OR₁₂ groupwherein R₁₂ represents a hydrogen atom, C1 through C6 alkyl oracidolytic/leaving group. As the above C1 through C6 alkyl groups,methyl, ethyl, isopropyl, t-butyl groups and the like can bespecifically exemplified. As R₁₂ in the above OR₁₂ groups, specificallythe same substituents as those exemplified as R₅ can be exemplified. Theletter, t represents any of the integers of 1 through 3 wherein R₁₁ maybe identical or different when t is 2 or more. The substituted sites ofR₁₃ are not especially limited but the para- or meta position of thealkenyl group is preferable in the case of the OR₁₂ group.

The configuration of the repeated unit (A21) represented by the generalformula (IV) and the repeated unit (A22) represented by the generalformula (V) in the above polymer chain (A2) is not especially limitedand may be any of the copolymers such as random polymerization, blockpolymerization and the like. Among them, the arm moiety having a polymerwherein the repeated units (A21) and (A22) are block-copolymerized by(A22) through (A21) sequentially from the central core is preferable.

The present invention can include repeated units other than the repeatedunits represented by the general formulae (I) through (V) as necessary.The repeated units are not especially limited so long as the repeatedunits are obtained from the compounds having double bond(s) capable ofcopolymerizing with the monomers corresponding to the general formulae(I) through (V). The repeated units not having acidic substituents suchas sulfonic groups, carboxyl groups, hydroxyphenol groups and the likeare preferred. As the monomers corresponding to the repeated units, thecompounds containing vinyl groups, the compounds containing (meth)acroyl groups and the like can be exemplified.

As compounds containing vinyl groups, aromatic vinyl compoundscontaining heteroatoms such as vinyl pyridine and the like, vinyl ketonecompounds such as methyl vinyl ketone, ethyl vinyl ketone and the like,vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether andthe like, alicyclic vinyl compounds containing hetero atoms such asvinyl pyrrolidone, vinyl lactam and the like can be specificallyexemplified.

Also, as the above compounds containing (meth) acroyl groups, (meth)acrylic amide or (meth) acrylonitrile and the like can be exemplified.

These vinyl group-containing compounds and (meth) acroylgroup-containing compounds can be used alone or as a mixture of two ormore. The repeated units obtained from these vinyl group-containingcompounds and (meth) acroyl group-containing compounds can be containedin the alkenylphenol copolymer of the present invention bycopolymerizing with the repeated units represented by the generalformulae (I) through (V) by random or by a block.

The number average molecular weight of the polymer (arm polymer) chainsconstituting the arm moiety (A) of the star block copolymer of thepresent invention is not especially limited, and specifically the rangeof from 1,000 to 100,000 can be exemplified. When the number averagemolecular weight of the polymer chains constituting the arm moiety (A)is from 1,000 to 100,000, the polymer chains having a single peakedratio (Mw/Mn) of the weight average molecular weight (Mw) to the numberaverage molecular weight (Mn) at the range of from 1.00 to 1.50 ispreferable.

As the central core of the star block copolymer of the presentinvention, polyfunctional coupling agents can be preferably exemplified,and, for example, a trifunctional or more compounds. Even in the case ofbifunctional compounds, if they can form trifunctional or more compoundswith polymerization, their use is not hampered. Especially, the centralcore wherein the polyfunctional coupling agent has a polymerizationcrosslinked structure is preferable.

As the above polyfunctional coupling agents, specifically, the compoundsrepresented by the general formula (VI) such as divinyl aromaticcompounds, trivinyl aromatic compounds and the like, diepoxide,diketone, dialdehyde, and the compounds represented by the followingformula (X):

(CR¹R₂X)nR³  (X)

wherein X represents a halogen atom, or a substituent selected from thegroup consisting of alkoxyl groups of carbon atoms of from 1 through 6and acyloxyl groups of carbon atoms of from 2 to 6; R¹ and R² eachrepresent hydrogen atoms or monovalent hydrocarbon groups of carbonatoms of from 1 to 6, and R¹ and R² may be identical or different; R³represents a multivalent aromatic hydrocarbon group capable of having nof substituents (CR¹R²X) or a multivalent aliphatic hydrocarbon groupwherein n represents any of the integers 3 through 6, can be included.Also the above polyfunctional coupling agents can include at least onecompound selected from the silane compounds and the like consisting ofthe following formulae.

The above divinyl aromatic compounds can include but are not especiallylimited to, for example, 1,3-divinyl benzene, 1,4-divinyl benzene,1,2-diisopropenyl benzene, 1,3-diidopropenyl benzene, 1,4-diisopropenylbenzene, 1,3-divinyl naphthalene, 1,8-divinyl naphthalene, 2,4-divinylphenyl, 1,2-divinyl-3,4-dimethyl benzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2′-divinyl-4-ethyl-4′-propyl biphenyl. These may be usedalone or in combination of two or more.

As such divinyl aromatic compounds, for example, those commerciallyavailable as mixtures with ethylvinyl benzene and the like can be usedas such so long as the above divinyl aromatic compound is a majorcomponent. Also, their purity may be increased by purification asneeded. Furthermore, a mixture with other double bond aromatic compoundscapable of polymerizing such as styrene can be used. In this case, themixture ratio of styrene is not specifically limited so long as it canform a crosslinked polymerization of the central core by mixing with thedivinyl aromatic compound, and is in the range of from 1 to 50%, andpreferably from 5 to 20% by weight.

The above trivinyl aromatic compounds can include but are not especiallylimited to, for example, 1,2,4-trivinyl benzene, 1,3,5-trivinylnaphthalene, 3,5,4′-trivinyl biphenyl, 1,5,6-trivinyl-3,7-diethylnaphthalene and the like. These may be used alone or in combination withtwo or more.

Also, as the above divinyl aromatic compounds and trivinyl aromaticcompounds, the chemical group represented by the general formula (VI)wherein the spacer is inserted between the vinyl group and the aromaticring can be preferably exemplified. More specifically, the compoundsrepresented below can be exemplified. These may be used alone or incombination with two or more.

Examples of the above diepoxide can include but are not especiallylimited to, for example, cyclohexane diepoxide, 1,4-pentane diepoxide,1,5-hexane diepoxide and the like. These may be used alone or incombination with two or more.

Examples of the above diketone can include but are not especiallylimited to, for example, 2,4-hexane dione, 2,5-hexane dione, 2,6-heptanedione and the like. These may be used alone or in combination with twoor more.

Examples of the above dialdehyde can include but are not especiallylimited to, for example, 1,4-butanedial, 1,5-pentanedial, 1,6-hexanedialand the like. These may be used alone or in combination with two ormore.

In the above general formula (X), X represents a halogen atom, analkoxyl group of carbon atoms of from 1 through 6, or acyloxy group ofcarbon atoms of from 2 through 6. The above halogen atoms can includechlorine, fluorine, bromine, iodine and the like. The above alkoxylgroups of carbon atoms of from 1 through 6 can include but are notespecially limited to, for example, methoxy, ethoxy, n- or iso-propoxyand the like. The above acyloxy groups of carbon atoms of from 2 through6 can include but are not especially limited to, for example, anacetyloxy group, a propionyloxy group, and the like.

In the above general formula (X), R¹ and R² each represent hydrogenatoms or monovalent hydrocarbon groups of carbon atoms of from 1 through6. R¹ and R² may be identical or different. Also, multiple R¹ andmultiple R² each may be identical or different. The above monovalenthydrocarbon groups of carbon atoms of from 1 through 6 can include butare not especially limited to, for example, methyl, ethyl, n- oriso-propyl groups and the like.

In the above general formula (X), R³ represents a multivalent aromatichydrocarbon group capable of having n of substituents (CR¹R²X) or amultivalent aliphatic hydrocarbon group as mentioned above. The letter nrepresents any of the integers of from 3 through 6. And as the compoundsrepresented by such general formula (X), the compounds represented bythe following chemical formulae can be specifically exemplified.

In addition to the above compounds exemplified, the compoundsrepresented by the following chemical formulae can be exemplified aspolyfunctional coupling agents.

The process for producing the star block copolymer of the presentinvention is not especially limited so long as it is a process byhomopolymerizing by anionic polymerization using an anionicpolymerization initiator as a polymerization initiator the compoundrepresented by the general formula (VII) wherein R₃, R₄, R₅, and q arethe same as mentioned above, subsequently copolymerizing apolyfunctional coupling agent, and eliminating protection of phenolhydroxyl groups; or by homopolymerizing by anionic polymerization usingan anionic polymerization initiator as a polymerization initiator acompound represented by the general formula (VII) or by copolymerizingwith a compound capable of copolymerizing with the compound representedby the general formula (VII), subsequently copolymerizing apolyfunctional coupling agent and further copolymerizing a compoundcapable of anion polymerizing, and then eliminating protection of phenolhydroxyl groups.

In the compound represented by the above formula (VII), R₃, R₄, R₅, andq are the same as mentioned above, and the same substituents can beexemplified. As compounds represented by the general formula (VII),specifically p-t-butoxystyrene, p-t-butoxy-α-methylstyrene,p-(tetrahydropyranyloxy)styrene,p-(tetrahydropyranyloxy)-α-methylstyrene, p-(1-ethoxyethoxy) styrene,p-(1-ethoxyethoxy)-α-methylstyrene and the like can be exemplified.These can be used alone or in a mixture of two or more.

As the anionic polymerization initiators used in the above anionicpolymerization, alkali metals or organic alkali metals can beexemplified. As alkali metals, lithium, sodium, potassium, cesium andthe like can be exemplified. As organic alkali metals, alkylated,allylated and arylated compounds of the above alkali metals can beexemplified. Specifically, ethyl lithium, n-butyl lithium, sec-butyllithium, tert-butyl lithium, sodium ethyl, lithium biphenyl, lithiumnaphthalene, lithium triphenyl, sodium naphthalene, α-methyl styrenesodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpenthyllithium and the like can be included.

The process for producing the star block copolymer of the presentinvention can include:

(1) a process by anion polymerizing the compound represented by thegeneral formula (VII) alone or anion polymerizing the compoundrepresented by the general formula (VII) and the compound represented bythe general formula (VIII) or anion polymerizing the compoundrepresented by the general formula (VII) and the compound having doublebonds capable of copolymerizing with the compound in the presence of ananionic polymerization initiator to synthesize the arm polymer,subsequently reacting the polyfunctional coupling agent, and theneliminating the entirety or parts of the protective groups of phenolhydroxyl groups from the resultant copolymer;

(2) a process by reacting the polyfunctional coupling agent to form thepolyfunctional core, subsequently anion polymerizing the compoundrepresented by said general formula (VII) alone or the compoundrepresented by the general formula (VII) and the compound represented bythe general formula (VIII) or the compound represented by the generalformula (VII) and the compound having double bonds capable ofcopolymerizing with the compound in the presence of an anionicpolymerization initiator to synthesize the arm polymer, and theneliminating the entirety or parts of the protective groups of phenolhydroxyl groups from the resultant copolymer; and

(3) a process by anion polymerizing the compound represented by thegeneral formula (VII) alone or the compound represented by the generalformula (VII) and the compound represented by the general formula (VIII)or the compound represented by the general formula (VII) and thecompound having double bonds capable of copolymerizing with the compoundto synthesize an arm polymer, subsequently reacting a polyfunctionalcoupling agent, further reacting the monomer capable of anionpolymerizing such as the compounds represented by the general formulae(IX), (VIII) and (IX) in the presence of an anionic polymerizationinitiator, and then eliminating the entirety or parts of the protectivegroups of phenol hydroxyl groups from the resultant copolymer. The above(1) and (3) are easy for controlling the reaction and preferable interms of producing the star block copolymer of which the structure iscontrolled.

Additionally, the star block copolymer of the present invention can beproduced by cation polymerizing the compound represented by the generalformula (VII) alone or the compound represented by the general formula(VII) and the compound represented by the general formula (VIII) or thecompound represented by the general formula (VII) and the compoundhaving double bonds capable of copolymerizing with the compound,subsequently reacting the polyfunctional coupling agent, and theneliminating entire or parts of protective groups of phenol hydroxylgroups from the resultant copolymer in the presence of a cationicpolymerization initiator such as triethylamine,2-chloro-2,4,4-trimethyl-1-pentene/TiCl₄ and the like.

The polymerization reaction to synthesize the arm polymer in the aboveprocess (1) or (3) can be conducted by either the method of dropping theanionic polymerization initiator into the monomer (mixed) solution orthe method of dropping the monomer (mixed) solution into the solutioncontaining the anionic polymerization initiator. The method of droppingthe monomer (mixed) solution into the solution containing the anionicpolymerization initiator is preferable in terms of ability to controlmolecular weight and molecular weight distribution. The syntheticreaction of the arm polymer is usually carried out in the organicsolvents under an inert gas atmosphere such as nitrogen, argon, and thelike at a temperature ranging from −100 to 50° C., and preferably from−100 to 40° C.

The organic solvents used in the synthetic reaction of the above armpolymer can include organic solvents usually used in anionicpolymerization such as anisole, hexamethylphosphoramide, and the like inaddition to aliphatic hydrocarbons such as n-hexane, n-heptane, and thelike, alicyclic hydrocarbons such as cyclohexane, cyclopentane and thelike, aromatic hydrocarbons such as benzene, toluene, and the like, andethers such as diethyl ether, tetrahydrofuran (THF), dioxane, and thelike. These can be used as a single solvent or a mixed solvent of two ormore. Among them, the mixed solvents of tetrahydrofuran with toluene,tetrahydrofuran with hexane, and tetrahydrofuran with methylcyclohexanecan be preferably exemplified in terms of polarity and solubility.

The polymerization forms of the arm polymer can include a randomcopolymer in which each component is statistically distributedthroughout the entirety of the copolymer chain, partial block copolymer,and complete block copolymer. Each of these can be synthesized byselecting the compound represented by the general formula (VII)described above and the additional method of vinyl aromatic compound andthe like. For example, the random copolymer can be synthesized bypolymerization by adding the mixture of the compound represented by thegeneral formula (VII) and the vinyl aromatic compound into a reactionsystem. The partial block copolymer can be synthesized by previouslypolymerizing the entirety of either one and subsequently continuingpolymerization by adding the other mixture or by previously polymerizingpartially either one and subsequently continuing polymerization byadding the mixture of both. The complete block copolymer can besynthesized by polymerization by sequentially adding the compoundrepresented by the general formula (VII) and the vinyl aromatic compoundinto the reaction system.

The reaction of the star block copolymer of which a branched polymerchain is the resultant arm polymer can be carried out by adding theaforementioned polyfunctional coupling agent to the reaction solutionafter completion of the synthetic reaction of the arm polymer. Thepolymer of which the structure is controlled and the distribution ofmolecular weight is narrow can be obtained by usually conducting thereaction in the organic solvent under an inert gas atmosphere such asnitrogen, argon, and the like at a temperature ranging from −100° C. to50° C., and preferably from −70° C. to 40° C. Such generation reactionof the star block copolymer can be carried out subsequently in thesolvent used to form the arm polymer, can be carried out in the solventof which composition is changed by adding other solvents, or carried outby replacing the solvent to the other solvent. As such solvents, thesame solvents can be used as those used in the synthetic reaction of thearm polymer.

In the process producing the star block copolymer of the presentinvention, the molar ratio [(C)/(D)] is preferably from 0.1 to 10 forthe polyfunctional coupling agent (C) to an active end of the polymerchain homopolymerizing the compound represented by the general formula(VII) or an active end (D) of the polymer chain copolymerizing thecompound represented by the formula (VII) and the compound capable ofcopolymerizing by anionic polymerization using the anionicpolymerization initiator as the polymerization initiator. When polyvinylcompounds such as divinyl benzene and the like are used as thepolyfunctional coupling agent, the quantity of the polyvinyl compoundsto be added is preferably in the range from 0.1 to 10 equivalents, andpreferably from 1 to 10 equivalents based on the amount of the activeend of the arm polymer chain. The reaction of the arm polymer chain withthe polyfunctional coupling agent can employ either the method in whichthe polyfunctional coupling agent is added to the arm polymer chainhaving the active end or the method in which the arm polymer chainhaving the active end is added to the polyfunctional coupling agent.

The number of arms of the star block copolymer is determined dependingon an additional quantity of the polyvinyl compound, reactiontemperature, and reaction period, and usually multiple star blockcopolymers with different numbers of the arm are simultaneouslygenerated by influences of different reactivity of living polymer endsand vinyl groups and steric hindrance. As the star block copolymer ofthe present invention, those having three or more of the arm arepreferred. The ratio (Mw/Mn) of the weight average molecular weight (Mw)to the number average molecular weight (Mn) of the generated star blockcopolymer is preferably in the range of from 1.00 to 1.50, and thenumber average molecular weight of the star block copolymer ispreferably from 3,000 to 300,000.

In the process (3) wherein new arm polymer chains are formed by reactingthe monomers capable of anion polymerizing to the central core(polyfunctional core) having the active end formed by reacting the armpolymer chain previously adjusted with the polyfunctional couplingagent, the star block copolymer having different types of arm polymerchains can be produced. The monomer capable of directly polymerizing canbe reacted to the active end present in the central core. Also themonomer can be reacted after reaction of the compounds such as diphenylethylene, stilbene, and the like or after the addition of alkali metalssuch as lithium chloride or metallic salts of alkali earth metals. Thelatter is sometimes advantageous in controlling the entire structure ofthe generated star block copolymer because the polymerization reactionis processed slowly when a highly reactive monomer such as acrylatederivatives is reacted. Also the above reaction can be carried outsubsequently in the solvent used to form the central core having theactive end, can be carried out in the solvent of which composition ischanged by adding other solvents, or carried out by replacing thesolvent to the other solvent. As such solvent, the same solvents can beexemplified as those used for synthesis of the arm polymer. Also, it ispossible that random copolymerized polymer chains are made by mixing andreacting two types of monomers as the arm polymer chain newly introducedfor the active end of the central core in the process (3) or as the armpolymer chain in the process (2) and that block polymer chains are madeby sequentially adding two types of monomers. It is also possible thatfunctional groups are introduced to the ends by adding carbon dioxide,epoxy and the like after completion of the reaction.

The reaction eliminating protective groups of phenol hydroxyl groupsfrom such a resultant copolymer and generating alkenylphenol skeletonsis carried out in the presence of the mixed solvent of one or more ofalcohols such as methanol, ethanol and the like, ketones such asacetone, methylethyl ketone and the like, multivalent alcoholderivatives such as methyl cellosolve, ethyl cellosolve and the like,water and the like, using an acid reagent such as hydrochloric acid,sulfuric acid, hydrochloric gas, hydrobromic gas, p-toluene sulfonate,1,1,1-trifluoro acetate, bisulfate represented by the following formula:XHSO₄ wherein X represents an alkali metal such as Li, Na, K and thelike as a catalyst at a temperature ranging from room temperature to150° C. in addition to the solvents exemplified by the polymerizationreaction.

In this reaction, the protective groups of phenol hydroxyl groups areselectively eliminated entirely or partially by appropriately combiningthe type and concentration of the solvent, the type and additionalquantity of the catalyst, and the reaction temperature and period,thereby being capable of producing the alkenylphenol star blockcopolymer with narrow dispersion in the present invention of which thestructure is controlled.

Among the star block copolymers obtained as described above havingalkenylphenol skeletons of the present invention, the arm polymer issometimes contaminated in the final product due to incomplete reactionin the copolymer obtained from the reaction of the polyfunctionalcoupling agent with the arm polymer. In this case, it is possible thatthe arm polymer chain is eliminated as needed if physical properties ofthe star block copolymer are variable. The fractional reprecipitationcan be suitably exemplified as an eliminating method. In such fractionalreprecipitation, reprecipitation is performed preferably using a mixedsolvent of high and lower polymer-soluble solvents. In the mixed solventof high and lower polymer-soluble solvents, the method in which the starblock copolymer is heat-dissolved and cooled, the method in which thestar block copolymer is crystallized by dissolving in the highpolymer-soluble solvent followed by adding the lower polymer-solublesolvent, and the like can be exemplified. The latter method can be alsoperformed by appropriately heating the solvent. Lower alcohols such asmethanol, ethanol, and the like as the above highly soluble solvents andwater as the above lower soluble solvent are preferably exemplified inthe star block copolymer. The mixed ratio of both solvents is varieddepending on the star block copolymer to be purified. Its volume ratio[(highly polymer-soluble solvent)/(lower polymer-soluble solvent)] ispreferably in the range of from 90/10 to 10/90 and more preferably from80/20 to 20/80. The concentration of such solution is not especiallylimited, but for example, the range of from 1 to 50%, and morepreferably the range of from 2 to 30% can be exemplified. When it is 1%or less, the crystallized yield is decreased due to such amounts ofsolvent. When it is 50% or more, efficiency to eliminate impurities isdecreased. The objective star block copolymer can be taken in an almostpure form by repeating these manipulations several times.

Best Mode for Carrying Out the Invention

The present invention is described by examples in more detail below. Butthe technical scope of the present invention is not limited by thefollowing examples.

EXAMPLE 1

Under a nitrogen atmosphere, n-butyl lithium (50 mmol, abbreviated asNBL hereinafter) was added to a mixed solvent of toluene (750 g) andtetrahydrofuran (750 g, abbreviated as THF hereinafter), subsequentlyp-tert butoxystyrene (1 mol, abbreviated as PTBST hereinafter) wasdropped over one hour by stirring and maintaining a temperature at −40°C., and further the reaction was continued for one hour followed byconfirming the completion of the reaction by gas chromatography(abbreviated as GC hereinafter). At this step, an aliquot was taken fromthe reaction system and analyzed by gel permeation chromatography(abbreviated as GPC hereinafter) after stopping the reaction withmethanol. The resultant PTBST polymer was a monodisperse polymer with Mnof 3700 and Mw/Mn of 1.10.

Then while maintaining the temperature of the reaction system at −40°C., divinyl benzene (150 mmol, abbreviated as DVB hereinafter) was addedand the reaction was continued for an additional 4 hours followed byconfirming no residual monomer by GC. Then, the reaction was terminatedby adding methanol to the reaction system, and the reaction solution waspoured into excess amounts of methanol to precipitate a polymer. Afterfiltrating and washing, drying with reduced pressure at 60° C. for 15hours afforded a white powder polymer. The polymerization yield based onthe total monomers used was 99.5%. The GPC analysis of this polymershowed that it was a monodisperse polymer with Mn of 29000 and Mw/Mn of1.14.

Then the resultant polymer (10 g) was dissolved in a mixed solvent oftoluene/ethanol=1/1 (weight ratio) to make 25% solution, subsequentlysulfuric acid (1.4 g) was added and the reaction was carried out at 40°C. for 45 hours followed by pouring the reaction solution into excessamounts of water to precipitate a polymer. After filtrating and washing,drying with reduced pressure at 60° C. for 5 hours afforded 7.1 g of awhite powder polymer.

The infrared absorption spectra (abbreviated as IR hereinafter) and¹³CNMR of the polymers before and after the reaction were compared inthis reaction. In IR observation, the absorption at 890 cm⁻¹ derivedfrom t-butyl groups of poly-PTBST disappeared after the reaction, andbroad absorption around 3300 cm⁻¹ derived from hydroxyl groups was newlyobserved. The peaks around 77 ppm and 153 ppm derived from t-butylgroups of poly-PTBST disappeared after the reaction. The GPC analysis ofthe generated polymer showed that it was a monodisperse polymer with Mnof 26500 and Mw/Mn of 1.16.

Consequently, it was confirmed that the copolymerization reaction andfollowing elimination reaction were carried out as being set and thatthe alkenylphenol star block copolymer in which p-hydroxystyrene segmentis a main skeleton was generated.

EXAMPLE 2

Under a nitrogen atmosphere, 30 mmol of NBL was added to 2000 g of THF,1 mol of PTBST was dropped over one hour by stirring and maintaining thetemperature at −60° C., and the reaction was further continued for onehour followed by confirming the completion of the reaction by GC. Atthis step, an aliquot was taken from the reaction system and analyzed byGPC after stopping the reaction with methanol. The resultant PTBSTpolymer was a monodisperse polymer with Mn of 5700 and Mw/Mn of 1.10.Then, while maintaining the temperature of the reaction system at −60°C., 30 mmol of DVB was added, and the reaction was continued for anadditional 4 hours followed by confirming no residual monomer by GC.

Then, the reaction was terminated by adding methanol to the reactionsystem, and the reaction solution was poured into excess amounts ofmethanol to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 15 hours afforded a white powderpolymer. The polymerization yield based on the total monomers used was99.1%. The GPC analysis of this polymer showed that it is a mixture of apolymer with Mn of 35000 and Mw/Mn of 1.15 and a polymer with Mn of5700.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=4/1 (weight ratio) to make 25% solution, 3 g of concentratedhydrochloric acid was added, and the reaction was carried out at 50° C.for 30 hours. Then, the reaction solution was poured into excess amountsof water to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 5 hours afforded 6.9 g of a whitepowder polymer.

In this reaction, IR and NMR of the polymers before and after reactionwere determined. The peak derived from t-butoxy groups of the PTBSTsegments was confirmed to disappear as in the case of Example 1. The GPCanalysis of the generated polymer showed that it was a mixture of apolymer with Mn of 32000 and Mw/Mn of 1.19 and a polymer with Mn of5100.

Consequently, it was confirmed that the copolymerization reaction andfollowing elimination reaction were carried out as being set and thatthe alkenylphenol star block copolymer in which p-hydroxystyrene segmentis a main skeleton was generated.

EXAMPLE 3

Under a nitrogen atmosphere, 20 mmol of NBL was added to a mixed solventof 1200 g of THF and 300 g of hexane, 1 mol of PTBST was dropped overone hour by stirring and maintaining a temperature at −60° C., and thereaction was further continued for one hour followed by confirming thecompletion of the reaction by GC. At this step, an aliquot was takenfrom the reaction system and analyzed by GPC after stopping the reactionwith methanol. The resultant PTBST polymer was a monodisperse polymerwith Mn of 8900 and Mw/Mn of 1.07.

Then, after raising the temperature of the reaction system up −40° C., amixture of 96 mmol of DVB and 4 mmol of ethylvinyl benzene was added andthe reaction was continued for an additional 4 hours followed byconfirming no residual monomer by GC. Then, the reaction was terminatedby adding methanol to the reaction system, and the reaction solution waspoured into excess amounts of methanol to precipitate a polymer. Afterfiltrating and washing, drying with reduced pressure at 60° C. for 15hours afforded a white powder polymer. The polymerization yield based onthe total monomers used was 99.5%. The GPC analysis of this polymershowed that it was a mixture of a polymer with Mn of 70000 and Mw/Mn of1.21 and a polymer with Mn of 8900.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent oftoluene/ethanol=1/2 (weight ratio) to make 25% solution, 3 g of sulfuricacid was added, and the reaction was carried out at 40° C. for 45 hours.Then, the reaction solution was poured into excess amounts of water toprecipitate a polymer. After filtrating and washing, drying with reducedpressure at 60° C. for 5 hours afforded 7.0 g of a white powder polymer.

In this reaction, IR and NMR of the polymers before and after reactionwere determined. The peak derived from t-butoxy groups of the PTBSTsegments was confirmed to disappear as in the case of Example 1. The GPCanalysis of the generated polymer showed that it was a mixture of apolymer with Mn of 64000 and Mw/Mn of 1.22 and a polymer with Mn of 8000(10%). Consequently, it was confirmed that the copolymerization reactionand following elimination reaction were carried out as being set andthat the alkenylphenol star polymer in which p-hydroxystyrene segment isa main skeleton was generated.

The mixture (3.5 g) obtained as described above was added to a mixedsolvent of purified water/methanol (volume ratio: 1/1) so that itsconcentration is 2% by weight, heated and dissolved, subsequently leftto room temperature and crystallized and then filtrated to yield 3.0 gof crystal. The analysis of the crystal using GPC showed that theresidual arm polymer was 0.35%.

Also, 3.5 g of the mixture obtained as described above was dissolved in35 ml of methanol and then 35 ml of purified water was added tocrystallize followed by filtrating to yield 3.2 g of crystal. Theanalysis of the crystal using GPC showed that the residual arm polymerwas 4.26%.

Consequently, it was confirmed that the copolymerization reaction andfollowing elimination reaction were carried out as being set and thatthe alkenylphenol star polymer in which p-hydroxystyrene segment is amain skeleton was generated.

EXAMPLE 4

Under a nitrogen atmosphere, 29 mmol of NBL was added to 2000 g of THF,subsequently a mixture of 1 mol of PTBST and 0.3 mole of styrene wasdropped over one hours by stirring and maintaining the temperature at−50° C., and the reaction was continued for an additional one hourfollowed by confirming the completion of the reaction by GC. At thisstep, PTBST/styrene polymer was a monodisperse polymer with Mn of 7200and Mw/Mn of 1.05. Then, after raising the temperature of the reactionsystem up −30° C., 30 mmol of DVB was added and the reaction wascontinued for an additional 5 hours followed by confirming thecompletion of the reaction by GC.

Then, the reaction was terminated by adding methanol to the reactionsystem, and the reaction solution was poured into excess amounts ofmethanol to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 15 hours afforded a white powderpolymer. The polymerization yield based on the total monomers used was99.3%. The GPC analysis of this polymer showed that it is a mixture of amonodisperse polymer with Mn of 63000 and Mw/Mn of 1.20 and a polymerwith Mn of 7200.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=1/1 (weight ratio) to make 25% solution, 3 g of sodiumhydrogen sulfate was added and the reaction was carried out at 50° C.for 20 hours. Subsequently, the reaction solution was filtrated toeliminate sodium hydrogen sulfate. The filtrate was poured into excessamounts of water to precipitate a polymer. After filtrating and washing,drying with reduced pressure at 60° C. for 5 hours afforded 7.1 g of awhite powder polymer. In this reaction, IR and NMR of the polymersbefore and after reaction were determined. The peak derived fromt-butoxy groups of the PTBST segments was confirmed to disappear as inthe case of Example 1. The GPC analysis of the generated polymer showedthat it was a mixture of a polymer with Mn of 56000 and Mw/Mn of 1.24and a polymer with Mn of 6500.

Consequently, it was confirmed that the copolymerization reaction andelimination reaction were carried out as being set and that thealkenylphenol star polymer in which a random copolymer ofp-hydroxystyrene and styrene is a main skeleton was generated.

EXAMPLE 5

Under a nitrogen atmosphere, 40 mmol of NBL was added to a mixed solventof 1000 g of toluene and 1000 g of THF, subsequently 1M of PTBST wasdropped over one hour by stirring and maintaining a temperature at −40°C., and the reaction was continued for an additional one hour followedby confirming the completion of the reaction by GC. At this step, thePTBST polymer was a monodisperse polymer with Mn of 4500 and Mw/Mn of1.11. Then, 0.3 mol of styrene was dropped over 15 min, and the reactionwas continued for an additional one hour followed by confirming thecompletion of the reaction by GC. At this step, the PTBST/styrene blockcopolymer was a monodisperse polymer with Mn of 5300 and Mw/Mn of 1.09.Finally, while maintaining the temperature of the reaction system at−40° C., 120 mmol of DVB was added and the reaction was continued for anadditional 5 hours followed by confirming the completion of the reactionby GC.

Then, the reaction was terminated by adding methanol to the reactionsystem, and the reaction solution was poured into excess amounts ofmethanol to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 15 hours afforded a white powderpolymer. The polymerization yield based on the total monomers used was99.3%. The GPC analysis of this polymer showed that it was amonodisperse polymer with Mn of 34000 and Mw/Mn of 1.18.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=2/1 (weight ratio) to make 25% solution, 3 g of sodiumhydrogen sulfate was added and the reaction was carried out at 50° C.for 20 hours. Subsequently, the reaction solution was filtrated toeliminate sodium hydrogen sulfate. The filtrate was poured into excessamounts of water to precipitate a polymer. After filtrating and washing,drying with reduced pressure at 60° C. for 5 hours afforded 7.2 g. of awhite powder polymer. In this reaction, IR and NMR of the polymersbefore and after reaction were determined. The peak derived fromt-butoxy groups of the PTBST segments was confirmed to disappear as inthe case of Example 1. The GPC analysis of the generated polymer showedthat it was a monodisperse polymer with Mn of 30000 and Mw/Mn of 1.22.

Consequently, it was confirmed that the copolymerization reaction andelimination reaction were carried out as being set and that thealkenylphenol star polymer in which a block copolymer ofp-hydroxystyrene segments and styrene segments is a main skeleton wasgenerated.

EXAMPLE 6

Under a nitrogen atmosphere, 30 mmol of NBL was added to 2000 g of THF,1 mol of PTBST was dropped over one hour by stirring and maintaining atemperature at −60° C., and the reaction was further continued for onehour followed by confirming the completion of the reaction by GC. Atthis step, an aliquot was taken from the reaction system and analyzed byGPC after stopping the reaction with methanol. The resultant polymer wasa monodisperse polymer with Mn of 6100 and Mw/Mn of 1.12.

Then, while maintaining the temperature of the reaction system at −60°C., 90 mmol of DVB was added, and the reaction was continued for anadditional 3 hours followed by confirming no residual monomer by GC. Atthis step, an aliquot was taken from the reaction system and analyzed byGPC after stopping the reaction with methanol. The resultant polymer wasa monodisperse polymer with Mn of 45100 and Mw/Mn of 1.16. Then, whilemaintaining a temperature of the reaction system at −60° C., 45 mmol of1,1-diphenyl ethylene (abbreviated as DPE hereinafter) was added andaged for 30 min. Subsequently, 0.43 mol of tert-butyl methacrylate(abbreviated as t-BMA hereinafter) was added and the reaction wascontinued for an additional one hour. Finally, the reaction wasterminated by adding methanol to the reaction system, and the reactionsolution was poured into excess amounts of methanol to precipitate apolymer. After filtrating and washing, drying with reduced pressure at60° C. for 15 hours afforded a white powder polymer. The polymerizationyield based on the total monomers used was 99.1%. The GPC analysis ofthis polymer showed that it was a monodisperse polymer with Mn of 46400and Mw/Mn of 1.20.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=4/1 (weight ratio) to make 25% solution, 2 g of concentratedhydrochloric acid was added, and the reaction was carried out at 50° C.for 30 hours. Then, the reaction solution was poured into excess amountsof water to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 5 hours afforded 7.2 g of a whitepowder polymer.

In this reaction, infrared absorption spectrum (abbreviated as IRhereinafter) and NMR of polymers before and after the reaction werecompared. In IR observation, absorption at 890 cm⁻¹ derived from t-butylgroups of poly-PTBST disappeared after the reaction, and broadabsorption of approximately 3300 cm⁻¹ derived from hydroxyl groups wasnewly observed. The peak around 77 ppm derived from t-butyl groups ofpoly-PTBST disappeared after the reaction. The GPC analysis of thegenerated polymer showed that it was a polymer with Mn of 42000 andMw/Mn of 1.21.

EXAMPLE 7

Under a nitrogen atmosphere, 23 mmol of NBL was added to a mixed solventof 1600 g of toluene and 400 g of THF, and 1 mol of PTBST was droppedover one hour by stirring and maintaining a temperature at −40° C. Thereaction was continued for an additional one hour and completion of thereaction was confirmed by GC. At this step, an aliquot was taken fromthe reaction system and analyzed by GPC after stopping the reaction withmethanol. The resultant PTBST polymer was a monodisperse polymer with Mnof 7900 and Mw/Mn of 1.07.

Then, while maintaining the temperature of the reaction system at −40°C., 50 mmol of DVB was added, and the reaction was continued for anadditional 3 hours followed by confirming no residual monomer by GC. Atthis step, an aliquot was taken from the reaction system and analyzed byGPC after stopping the reaction with methanol. The resultant polymer wasa mixture of a monodisperse polymer with Mn of 61500 and Mn/Mw of 1.17and a polymer with Mn of 7900. Next, while maintaining the temperatureof the reaction system at −40° C., 28 mmol of DPE was added and aged for30 min. Subsequently, 0.2 mol of t-BMA was added and the reaction wascontinued for an additional one hour. Finally, the reaction wasterminated by adding methanol to the reaction system, and the reactionsolution was poured into excess amounts of methanol to precipitate apolymer. After filtrating and washing, drying with reduced pressure at60° C. for 15 hours afforded a white powder polymer. The polymerizationyield based on the total monomers used was 99.8%. The GPC analysis ofthis polymer showed that it was a mixture of a monodisperse polymer withMn of 63000 and Mw/Mn of 1.21 and a polymer with Mn of 7900. Next, 10 gof the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=3/1 (weight ratio) to make 25% solution, 2.4 g ofconcentrated hydrochloric acid was added, and the reaction was carriedout at 50° C. for 30 hours. Then, the reaction solution was poured intoexcess amounts of water to precipitate a polymer. After filtrating andwashing, drying with reduced pressure at 60° C. for 5 hours afforded 6.9g of a white powder polymer.

IR and NMR of polymers before and after the reaction altered as in thecase of Example 1. The GPC analysis of the generated polymer showed thatit was a mixture of a monodisperse polymer with Mn of 56000 and Mw/Mn of1.21 and a polymer with Mn of 7100.

EXAMPLE 8

Under a nitrogen atmosphere, 18 mmol of NBL was added to a mixed solventof 1000 g of toluene and 1000 g of THF, and 0.9 mol of PTBST was droppedover one hour by stirring and maintaining a temperature at −40° C. Thereaction was continued for an additional one hour and completion of thereaction was confirmed by GC. At this step, an aliquot was taken fromthe reaction system and analyzed by GPC after stopping the reaction withmethanol. The resultant PTBST polymer was a monodisperse polymer with Mnof 9100 and Mw/Mn of 1.09.

Then, while raising the temperature of the reaction system to −20° C., amixture of 54 mmol of DVB and 13 mmol of styrene was added, and thereaction was continued for an additional 3 hours followed by confirmingno residual monomer by GC. At this step, an aliquot was taken from thereaction system and analyzed by GPC after stopping the reaction withmethanol. The resultant polymer was a mixture of a monodisperse polymerwith Mn of 57000 and Mn/Mw of 1.17 and a polymer with Mn of 9100. Next,while maintaining a temperature of the reaction system at −20° C., 21mmol of DPE was added and aged for 30 min. Subsequently, 0.1 mol oft-BMA was added and the reaction was continued for an additional onehour. Finally, the reaction was terminated by adding methanol to thereaction system, and the reaction solution was poured into excessamounts of methanol to precipitate a polymer. After filtrating andwashing, drying with reduced pressure at 60° C. for 15 hours afforded awhite powder polymer. The polymerization yield based on the totalmonomers used was 99.6%. The GPC analysis of this polymer showed that itwas a mixture of a monodisperse polymer with Mn of 58200 and Mw/Mn of1.21 and a polymer with Mn of 9100.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=1/1 (weight ratio) to make 25% solution, 0.5 g ofconcentrated sulfuric acid was added, and the reaction was carried outat 50° C. for 30 hours. Then, the reaction solution was poured intoexcess amounts of water to precipitate a polymer. After filtrating andwashing, drying with reduced pressure at 60° C. for 5 hours afforded 6.9g of a white powder polymer.

IR and NMR of polymers before and after the reaction altered as in thecase of Example 1. The GPC analysis of the generated polymer showed thatit was the mixture of a monodisperse polymer with Mn of 51200 and Mw/Mnof 1.20 and a polymer with Mn of 8100.

EXAMPLE 9

Under a nitrogen atmosphere, 50 mmol of NBL was added to a mixed solventof 750 g of toluene and 750 g of THF, and 1 mol of PTBST was droppedover one hour by stirring and maintaining a temperature at −40° C. Thereaction was continued for an additional one hour and completion of thereaction was confirmed by GC. At this step, an aliquot was taken fromthe reaction system and analyzed by GPC after stopping the reaction withmethanol. The resultant PTBST polymer was a monodisperse polymer with Mnof 3700 and Mw/Mn of 1.10.

Then, while maintaining a temperature of the reaction system at −40° C.,150 mmol of DVB was added, and the reaction was continued for additional4 hours followed by confirming no residual monomer by GC. Then, thereaction was terminated by adding methanol to the reaction system, andthe reaction solution was poured into excess amounts of methanol toprecipitate a polymer. After filtrating and washing, drying with reducedpressure at 60° C. for 15 hours afforded a white powder polymer. Thepolymerization yield based on the total monomers used was 99.5%. The GPCanalysis of this polymer showed that it was a monodisperse polymer withMn of 29000 and Mw/Mn of 1.14.

Then, 10 g of the resultant polymer was dissolved in a mixed solvent oftoluene/ethanol=1/1 (weight ratio) to make 25% solution, and 1.4 g ofsulfuric acid was added to start debutylation. The reaction was carriedout at from. 65 to 70° C. An aliquot of the reaction solution was takenand its IR spectrum was determined to follow the reaction. Afterconfirming that the elimination quantity reached a given quantity, thereaction system was rapidly cooled in an ice bath, and the reactionsolution was poured into excess amounts of water to precipitate apolymer. After filtrating and washing, drying with reduced pressure at70° C. for 5 hours afforded 7.0 g of a white powder polymer.

The GPC analysis of this polymer showed that it was a monodispersepolymer with Mn of 27000 and Mw/Mn of 1.15. The ratio ofpara-hydroxystyrene (PHS) unit/PTBST unit obtained by NMR was 0.88/0.12(molar ratio).

EXAMPLE 10

Under a nitrogen atmosphere, 23 mmol of NBL was added to a mixed solventof 1600 g of toluene and 400 g of THF, and 1 mol of PTBST was droppedover one hour by stirring and maintaining a temperature at −40° C. Thereaction was continued for an additional one hour and completion of thereaction was confirmed by GC. At this step, an aliquot was taken fromthe reaction system and analyzed by GPC after stopping the reaction withmethanol. The resultant PTBST polymer was a monodisperse polymer with Mnof 7900 and Mw/Mn of 1.07.

Then, while maintaining the temperature of the reaction system at −40°C., 50 mmol of DVB was added, and the reaction was continued for anadditional 3 hours followed by confirming no residual monomer by GC. Atthis step, an aliquot was taken from the reaction system and analyzed byGPC after stopping the reaction with methanol. The resultant polymer wasthe mixture of a monodisperse polymer with Mn of 55300 and Mn/Mw of 1.17and a polymer with Mn of 7900. Next, while maintaining a temperature ofthe reaction system at −40° C., 28 mmol of DPE was added and aged for 30min. Further 0.2 mol of t-BMA was added and the reaction was continuedfor 2 hours. Finally, the reaction was terminated by adding methanol tothe reaction system, and the reaction solution was poured into excessamounts of methanol to precipitate a polymer. After filtrating andwashing, drying with reduced pressure at 60° C. for 15 hours afforded awhite powder polymer. The polymerization yield based on the totalmonomers used was 99.8%. The GPC analysis of this polymer showed that itwas a mixture of a monodisperse polymer with Mn of 56500 and Mw/Mn of1.21 and a polymer with Mn of 7900.

Next, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=3/1 (weight ratio) to make 25% solution, and 2.4 g ofconcentrated hydrochloric acid was added to start debutylation at 50° C.The reaction was carried out at from 65 to 70° C. An aliquot of thereaction solution was taken and its IR spectrum was determined to followthe reaction. After confirming that the elimination quantity reached agiven quantity, the reaction system was rapidly cooled in an ice bath,and the reaction solution was poured into excess amounts of water toprecipitate a polymer. After filtrating and washing, drying with reducedpressure at 70° C. for 5 hours afforded 7.0 g of a white powder polymer.

The GPC analysis of this polymer showed that it was a monodispersepolymer with Mn of 49000 and Mw/Mn of 1.20. The ratio of PHS unit/PTBSTunit obtained by NMR was 0.90/0.10 (molar ratio).

EXAMPLE 11

Under a nitrogen atmosphere, 29 mmol of NBL was added to 2000 g of THF,and the mixture of 1 mol of PTBST and 0.3 mol of styrene were droppedover one hour by stirring and maintaining a temperature at −50° C. Thereaction was continued for an additional one hour and completion of thereaction was confirmed by GC. At this step, the PTBST/styrene polymerwas a monodisperse polymer with Mn of 7200 and Mw/Mn of 1.05. Then,after raising the temperature of the reaction system to −30° C., 30 mmolof DVB was added and the reaction was continued for an additional 5hours followed by confirming completion of the reaction by GC.

Then, the reaction was terminated by adding methanol to the reactionsystem, and the reaction solution was poured into excess amounts ofmethanol to precipitate a polymer. After filtrating and washing, dryingwith reduced pressure at 60° C. for 15 hours afforded a white powderpolymer. The polymerization yield based on the total monomers used was99.3%. The GPC analysis of this polymer showed that it was the mixtureof a monodisperse polymer with Mn of 47000 and Mw/Mn of 1.20 and apolymer with Mn of 7200.

Next, 10 g of the resultant polymer was dissolved in a mixed solvent ofTHF/ethanol=1/1 (weight ratio) to make 25% solution, and 1.4 g ofsulfuric acid was added to start debutylation. The reaction was carriedout at from 65 to 70° C. An aliquot of the reaction solution was takenand its IR spectrum was determined to follow the reaction. Afterconfirming that the elimination quantity reached a given quantity, thereaction system was rapidly cooled in an ice bath, and the reactionsolution was poured into excess amounts of water to precipitate apolymer. After filtrating and washing, drying with reduced pressure at70° C. for 5 hours afforded 7.0 g of a white powder polymer.

The GPC analysis of this polymer showed that it was a monodispersepolymer with Mn of 43500 and Mw/Mn of 1.15. The ratio ofpara-hydroxystyrene (PHS) unit/PTBST unit obtained by NMR was 0.88/0.12(molar ratio).

Consequently, it could be confirmed that the copolymerization reactionand the elimination reaction were carried out as being set and that thealkenylphenol star polymer in which a random copolymer ofp-hydroxystyrene and styrene is a main skeleton was generated.

INDUSTRIAL APPLICABILITY

The star block copolymer having an arm moiety of alkenylphenol moietycan be obtained by the present invention of which molecular weightdistribution is narrow, the structure is controlled and utilization isanticipated as a resist material for excimer lasers and electron beams.

What is claimed is:
 1. A star block copolymer characterized in that anarm moiety (A) comprises a polymer chain (A1) consisting of only arepeated unit represented by the general formula (I):

wherein R₁ represents a hydrogen atom or a methyl group; R₂ represents ahydrogen atom or a C1 through C6 alkyl group; and p represents 1 or 2wherein R₂ may be identical or different when p is 2, in the star blockcopolymer having the arm moiety composed of a central core and polymerchains extending from the central core; or having a repeated unitrepresented by one of the general formulae (I) and (II):

wherein R₃ represents a hydrogen atom or a methyl group; R₄ represents aC1 through C6 alkyl group; R₅ represents an acidolytic/leaving group; qrepresents 0, 1 or 2 wherein R₄ may be identical or different when q is2; the general formulae (I) and (III):

wherein R₆ represents a hydrogen atom, a methyl group or an aryl groupwhich may have substituents; R₇ represents a C1 through C6 alkyl group;r represents 0, 1 or 2 wherein R₇ may be identical or different when ris 2; and the general formulae (I), (II) and (III):

wherein R₃, R₄, R₅, and q are the same as mentioned above.
 2. The starblock copolymer according to claim 1, characterized in that the armmoiety (A) has the polymer chain (A1) and a polymer chain (A2) havingrepeated units (A21) represented by one of: the general formula (IV):

wherein R₈ represents a hydrogen atom or a methyl group; and R₉represents a hydrogen atom, a C1 through C12 alkyl group, a hydrocarbongroup having alicyclic skeletons of C3 or more which may havesubstituents, an alkyl group having hydrocarbon groups having thealicyclic skeletons, or a heterocyclic group; and the general formula(IV) and repeated units (A22) represented by the general formula (V):

wherein R₁₀ is a hydrogen atom, a methyl group, or an aryl group whichmay have substituents; R₁₁ represents a C1 through C6 alkyl group, orOR₁₂ group wherein R₁₂ represents a hydrogen atom, a C1 through C6 alkylgroup, or an acidolytic/leaving group; and t represents an integer of 0or from 1 through 3 wherein R₁₁ may be identical or different when t is2 or more.
 3. The star block copolymer according to claim 2,characterized in that the polymer chain (A2) is a block copolymerized by(A22) through (A21) sequentially from the central core.
 4. The starblock copolymer according to claim 1, characterized in that the numberaverage molecular weight of the polymer chains constituting the armmoiety is from 1,000 to 100,000 and the ratio (Mw/Mn) of the weightaverage molecular weight(Mw) to the number average molecular weight(Mn)is in the range of from 1.00 to 1.50.
 5. The star block copolymeraccording to claim 1, characterized in that the central core is a corecrosslinked with a polyfunctional coupling agent.
 6. The star blockcopolymer according to claim 5, characterized in that the polyfunctionalcoupling agent is a compound having at least two polymerization doublebonds per molecule.
 7. The star block copolymer according to claim 5,characterized in that the polyfunctional coupling agent is a compoundrepresented by the general formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2; and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 8. The star block copolymeraccording to claim 1, characterized in that the number average molecularweight is from 3,000 to 200,000.
 9. A process for producing the starblock copolymer according to claim 1, characterized in that by anionicpolymerization using an anionic polymerization initiator as apolymerization initiator, after a compound represented by the generalformula (VII):

wherein R₃, R₄, R₅ and q are the same as mentioned above ishomopolymerized or after the compound represented by the general formula(VII) and a compound capable of copolymerizing are copolymerized,further a polyfunctional coupling agent (C) is copolymerized, and thenprotective groups of phenol hydroxyl groups are eliminated.
 10. Theprocess for producing the star block copolymer according to claim 9,characterized in that the molar ratio is from 0.1 to 10 of thepolyfunctional coupling agent (C) to an active end of the polymer chainhomopolymerizing the compound represented by the general formula (VII)or an active end (D) of the polymer chain copolymerizing a compoundcapable of copolymerizing with the compound represented by the generalformula (VII) by anionic polymerization using an anionic polymerizationinitiator as a polymerization initiator.
 11. The process for producingthe star block copolymer according to claim 9, characterized in that thepolyfunctional coupling agent is a compound represented by the generalformula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2: and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 12. The process forproducing the star block copolymer according to claim 9, characterizedin that the compound capable of copolymerizing with the compoundrepresented by the general formula (VII) is a compound represented bythe general formula (VIII):

wherein R₆, R₇, and r are the same as mentioned above.
 13. The processfor producing the star block copolymer according to claim 9,characterized in that the compound capable of anion polymerizing is acompound represented by the general formula (IX):

wherein R₈ and R₉ are the same as mentioned above.
 14. A star blockcopolymer characterized in that an arm moiety (A) comprises a polymerchain (A1) having a repeated unit represented by one of the generalformula (I):

wherein R₁ represents a hydrogen atom or a methyl group; R₂ represents ahydrogen atom or a C1 through C6 alkyl group; and p represents 1 or 2wherein R₂ may be identical or different when p is 2, in the star blockcopolymer having the arm moiety composed of a central core and polymerchains extending from the central core; the general formulae (I) and(II):

wherein R₃ represents a hydrogen atom or a methyl group; R₄ represents aC1 through C6 alkyl group; R₅ represents an acidolytic/leaving group; qrepresents 0, 1 or 2 wherein R₄ may be identical or different when q is2; the general formulae (I) and (III):

wherein R₆ represents a hydrogen atom, a methyl group or an aryl groupwhich may have substituents; R₇ represents a C1 through C6 alkyl group;r represents 0, 1 or 2 wherein R₇ may be identical or different when ris 2; and the general formulae (I), (II) and (III):

wherein R₃, R₄, R₅, and q are the same as mentioned above, and whereinthe arm moiety (A) has the polymer chain (A1) and a polymer chain (A2)having repeated units (A21) represented by one of: the general formula(IV):

wherein R₈ represents a hydrogen atom or a methyl group; and R₉represents a hydrogen atom, a C1 through C12 alkyl group, a hydrocarbongroup having alicyclic skeletons of C3 or more which may havesubstituents, an alkyl group having hydrocarbon groups having thealicyclic skeletons, or a heterocyclic group; and the general formula(IV) and repeated units (A22) represented by the general formula (V):

wherein R₁₀ is a hydrogen atom, a methyl group, or an aryl group whichmay have substituents; R₁₁represents a C1 through C6 alkyl group, orOR₁₂ group wherein R₁₂ represents a hydrogen atom, a C1 through C6 alkylgroup, or an acidolytic/leaving group; and t represents an integer of 0or from 1 through 3 wherein R₁₁ may be identical or different when t is2 or more.
 15. The star block copolymer according to claim 14,characterized in that the polymer chain (A2) is a block copolymerized by(A22) through (A21) sequentially from the central core.
 16. The starblock copolymer according to claim 14, characterized in that the numberaverage molecular weight of the polymer chains constituting the armmoiety is from 1,000 to 100,000 and the ratio (Mw/Mn) of the weightaverage molecular weight(Mw) to the number average molecular weight(Mn)is in the range of from 1.00 to 1.50.
 17. The star block copolymeraccording to claim 14, characterized in that the central core is a corecrosslinked with a polyfunctional coupling agent.
 18. The star blockcopolymer according to claim 17, characterized in that thepolyfunctional coupling agent is a compound having at least twopolymerization double bonds per molecule.
 19. The star block copolymeraccording to claim 17, characterized in that the polyfunctional couplingagent is a compound represented by the general formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2; and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 20. The star block copolymeraccording to claim 14, characterized in that the number averagemolecular weight is from 3,000 to 200,000.
 21. A process for producingthe star block copolymer according to claim 14, characterized in that byanionic polymerization using an anionic polymerization initiator as apolymerization initiator, after a compound represented by the generalformula (VI):

wherein R₃, R₄, R₅ and q are the same as mentioned above ishomopolymerized or after the compound represented by the general formula(VII) and a compound capable of copolymerizing are copolymerized,further a polyfunctional coupling agent (C) is copolymerized, and thenprotective groups of phenol hydroxyl groups are eliminated.
 22. Theprocess for producing the star block copolymer according to claim 21,characterized in that the molar ratio is from 0.1 to 10 of thepolyfunctional coupling agent (C) to an active end of the polymer chainhomopolymerizing the compound represented by the general formula (VII)or an active end (D) of the polymer chain copolymerizing a compoundcapable of copolymerizing with the compound represented by the generalformula (VII) by anionic polymerization using an anionic polymerizationinitiator as a polymerization initiator.
 23. The process for producingthe star block copolymer according to claim 21, characterized in thatthe polyfunctional coupling agent is a compound represented by thegeneral formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈ R₁₉ and R₂₀ represent C1 throughC6 alkyl groups, or phenyl groups which may have substituents, OCO orCO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y may beidentical or different when w is 2; and u represents 2 or 3 wherein Y,R₁₃ and w may be identical or different.
 24. The process for producingthe star block copolymer according to claim 21, characterized in thatthe compound capable of copolymerizing with the compound represented bythe general formula (VII) is a compound represented by the generalformula (VIII):

wherein R₆, R₇, and r are the same as mentioned above.
 25. The processfor producing the star block copolymer according to claim 21,characterized in that the compound capable of anion polymerizing is acompound represented by the general formula (IX):

wherein R₈ and R₉ are the same as mentioned above.
 26. A star blockcopolymer characterized in that an arm moiety (A) comprises a polymerchain (A1) having a repeated unit represented by one of the generalformula (I):

wherein R₁ represents a hydrogen atom or a methyl group; R₂ represents ahydrogen atom or a C1 through C6 alkyl group; and p represents 1 or 2wherein R₂ may be identical or different when p is 2, in the star blockcopolymer having the arm moiety composed of a central core and polymerchains extending from the central core; the general formulae (I) and(II):

wherein R₃ represents a hydrogen atom or a methyl group; R₄ represents aC1 through C6 alkyl group; R₅ represents an acidolytic/leaving group; qrepresents 0, 1 or 2 wherein R₄ may be identical or different when q is2; the general formulae (I) and (III):

wherein R₆ represents a hydrogen atom, a methyl group or an aryl groupwhich may have substituents; R₇ represents a C1 through C6 alkyl group;r represents 0, 1 or 2 wherein R₇ may be identical or different when ris 2; and the general formulae (I), (II) and (III):

wherein R₃, R₄, R₅, and q are the same as mentioned above, characterizedin that by anionic polymerization using an anionic polymerizationinitiator as a polymerization initiator, after a compound represented bythe general formula (VII):

wherein R₃, R₄, R₅ and q are the same as mentioned above ishomopolymerized or after the compound represented by the general formula(VII) and a compound capable of copolymerizing are copolymerized,further a polyfunctional coupling agent (C) is copolymerized, and thenprotective groups of phenol hydroxyl groups are eliminated.
 27. The starblock copolymer according to claim 26, characterized in that the armmoiety (A) has the polymer chain (A1) and a polymer chain (A2) havingrepeated units (A21) represented by one of: the general formula (IV):

wherein R₈ represents a hydrogen atom or a methyl group; and R₉represents a hydrogen atom, a C1 through C12 alkyl group, a hydrocarbongroup having alicyclic skeletons of C3 or more which may havesubstituents, an alkyl group having hydrocarbon groups having thealicyclic skeletons, or a heterocyclic group; and the general formula(IV) and repeated units (A22) represented by the general formula (V):

wherein R₁₀ is a hydrogen atom, a methyl group, or an aryl group whichmay have substituents; R₁₁ represents a C1 through C6 alkyl group, orOR₁₂ group wherein R₁₂ represents a hydrogen atom, a C1 through C6 alkylgroup, or an acidolytic/leaving group; and t represents an integer of 0or from 1 through 3 wherein R₁₁ may be identical or different when t is2 or more.
 28. The star block copolymer according to claim 27,characterized in that the polymer chain (A2) is a block copolymerized by(A22) through (A21) sequentially from the central core.
 29. The starblock copolymer according to claim 26, characterized in that the numberaverage molecular weight of the polymer chains constituting the armmoiety is from 1,000 to 100,000 and the ratio (Mw/Mn) of the weightaverage molecular weight(Mw) to the number average molecular weight(Mn)is in the range of from 1.00 to 1.50.
 30. The star block copolymeraccording to claim 26, characterized in that the central core is a corecrosslinked with a polyfunctional coupling agent.
 31. The star blockcopolymer according to claim 30, characterized in that thepolyfunctional coupling agent is a compound having at least twopolymerization double bonds per molecule.
 32. The star block copolymeraccording to claim 30, characterized in that the polyfunctional couplingagent is a compound represented by the general formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2; and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 33. The star block copolymeraccording to claim 26, characterized in that the number averagemolecular weight is from 3,000 to 200,000.
 34. The process for producingthe star block copolymer according to claim 26, characterized in thatthe molar ratio is from 0.1 to 10 of the polyfunctional coupling agent(C) to an active end of the polymer chain homopolymerizing the compoundrepresented by the general formula (VII) or an active end (D) of thepolymer chain copolymerizing a compound capable of copolymerizing withthe compound represented by the general formula (VII) by anionicpolymerization using an anionic polymerization initiator as apolymerization initiator.
 35. The process for producing the star blockcopolymer according to claim 26, characterized in that thepolyfunctional coupling agent is a compound represented by the generalformula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2; and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 36. The process forproducing the star block copolymer according to claim 26, characterizedin that the compound capable of copolymerizing with the compoundrepresented by the general formula (VII) is a compound represented bythe general formula (VIII):

wherein R₆, R₇, and r are the same as mentioned above.
 37. The processfor producing the star block copolymer according to claim 26,characterized in that the compound capable of anion polymerizing is acompound represented by the general formula (IX):

wherein R₈ and R₉ are the same as mentioned above.
 38. A star blockcopolymer characterized in that an arm moiety (A) comprises a polymerchain (A1) having a repeated unit represented by one of the generalformula (I):

wherein R₁ represents a hydrogen atom or a methyl group; R₂ represents ahydrogen atom or a C1 through C6 alkyl group; and p represents 1 or 2wherein R₂ may be identical or different when p is 2, in the star blockcopolymer having the arm moiety composed of a central core and polymerchains extending from the central core; the general formulae (I) and(II):

wherein R₃ represents a hydrogen atom or a methyl group; R₄ represents aC1 through C6 alkyl group; R₅ represents an acidolytic/leaving group; qrepresents 0, 1 or 2 wherein R₄ may be identical or different when q is2; the general formulae (I) and (III):

wherein R₆ represents a hydrogen atom, a methyl group or an aryl groupwhich may have substituents; R₇ represents a C1 through C6 alkyl group;r represents 0, 1 or 2 wherein R₇ may be identical or different when ris 2; and the general formulae (I), (II) and (III):

wherein R₃, R₄, R₅, and q are the same as mentioned above, and whereinthe central core is a core crosslinked with a polyfunctional couplingagent.
 39. The star block copolymer according to claim 38, characterizedin that the arm moiety (A) has the polymer chain (A1) and a polymerchain (A2) having repeated units (A21) represented by one of: thegeneral formula (IV):

wherein R₈ represents a hydrogen atom or a methyl group; and R₉represents a hydrogen atom, a C1 through C12 alkyl group, a hydrocarbongroup having alicyclic skeletons of C3 or more which may havesubstituents, an alkyl group having hydrocarbon groups having thealicyclic skeletons, or a heterocyclic group; and the general formula(IV) and repeated units (A22) represented by the general formula (V):

wherein R₁₀ is a hydrogen atom, a methyl group, or an aryl group whichmay have substituents; R₁₁ represents a C1 through C6 alkyl group, orOR₁₂ group wherein R₁₂ represents a hydrogen atom, a C1 through C6 alkylgroup, or an acidolytic/leaving group; and t represents an integer of 0or from 1 through 3 wherein R₁₁ may be identical or different when t is2 or more.
 40. The star block copolymer according to claim 39,characterized in that the polymer chain (A2) is a block copolymerized by(A22) through (A21) sequentially from the central core.
 41. The starblock copolymer according to claim 38, characterized in that the numberaverage molecular weight of the polymer chains constituting the armmoiety is from 1,000 to 100,000 and the ratio (Mw/Mn) of the weightaverage molecular weight(Mw) to the number average molecular weight(Mn)is in the range of from 1.00 to 1.50.
 42. The star block copolymeraccording to claim 38, characterized in that the polyfunctional couplingagent is a compound having at least two polymerization double bonds permolecule.
 43. The star block copolymer according to claim 38,characterized in that the polyfunctional coupling agent is a compoundrepresented by the general formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups, or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₈, and R₂₀ represent C1through C6 alkyl groups, or phenyl groups which may have substituents,OCO or CO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y maybe identical or different when w is 2; and u represents 2 or 3 whereinY, R₁₃ and w may be identical or different.
 44. The star block copolymeraccording to claim 38, characterized in that the number averagemolecular weight is from 3,000 to 200,000.
 45. A process for producingthe star block copolymer according to claim 38, characterized in that byanionic polymerization using an anionic polymerization initiator as apolymerization initiator, after a compound represented by the generalformula (VII):

wherein R₃, R₄, R₅ and q are the same as mentioned above ishomopolymerized or after the compound represented by the general formula(VII) and a compound capable of copolymerizing are copolymerized,further a polyfunctional coupling agent (C) is copolymerized, and thenprotective groups of phenol hydroxyl groups are eliminated.
 46. Theprocess for producing the star block copolymer according to claim 45,characterized in that the molar ratio is from 0.1 to 10 of thepolyfunctional coupling agent (C) to an active end of the polymer chainhomopolymerizing the compound represented by the general formula (VII)or an active end (D) of the polymer chain copolymerizing a compoundcapable of copolymerizing with the compound represented by the generalformula (VII) by anionic polymerization using an anionic polymerizationinitiator as a polymerization initiator.
 47. The process for producingthe star block copolymer according to claim 45, characterized in thatthe polyfunctional coupling agent is a compound represented by thegeneral formula (VI):

wherein R₁₃ represents a hydrogen atom or a methyl group; Y representsan oxygen atom, a sulfur atom, R₁₆N wherein R₁₆ represents a hydrogenatom, C1 through C6 alkyl groups or alkoxycarbonyl groups, a methylenegroup which may have substituents, a phenylene group which may havesubstituents, C(R₁₈R₁₉)O, C(R₁₈R₁₉)S, C(R₁₈R₁₉)N(R₂₀), OC(R₁₈R₁₉),SC(R₁₈R₁₉), N(R₂₀)C(R₁₈R₁₉) wherein R₁₈, R₁₉ and R₂₀ represent C1through C6 groups, or phenyl groups which may have substituents, OCO orCO₂CH₂; w represents an integer of 0 or from 1 to 2 wherein Y may beidentical or different when w is 2; and u represents 2 or 3 wherein Y,R₁₃ and w may be identical or different.
 48. The process for producingthe star block copolymer according to claim 45, characterized in thatthe compound capable of copolymerizing with the compound represented bythe general formula (VII) is a compound represented by the generalformula (VIII):

wherein R₆, R₇, and r are the same as mentioned above.
 49. The processfor producing the star block copolymer according to claim 45,caracterized in that the compound capable of anion polymerizing is acompound represented by the general formula (IX):

wherein R₈ and R₉ are the same as mentioned above.